Aminotriazine-formaldehyde condensation products and process of making same



UNITEDSTATES PATENT OFFICE FOBMALDEBYDE GON- DENBATION PRODUCTS AND PROCESS OF MAKING SAME Gustav Wldmer, Basel, Switzerland, assignor, by mesne assignments, to Ciba Products Corporation, Hoboken, N. 1., a corporation of New Jersey No Drawing. Application June 5. 1942. Serial No. 448,470. In Swltnerland July 29,1941

6 Claims. ((31. 260*72) The subject at the present invention is a process lincleic, and riclnoleic acids, as well as substituted for the manutacture ofhardenable reaction prodiatty acids, such as naphthenic acids, etc., or ucts, solnbleinorganlc solvents,o1 aminotriaziuepoll basic acids, such as succinlc acids, sebacic iornialdehydecondensation products, and comacid and the like. Instead of the free acid, deprisesreacting others e1 aminotrlazine-iormalde- 5 rivatives may be used, if desired, which react in hydecondensation products, preljerably'ot melthe same manner, for example, the anhydrides, amineei'ormaldehrde condensation products, with halides, etc.

semi-seed or unsaturated carboxylicacids of the It is advisable to c y out e reaction in t (attracid series, ,1 absenceot water, since otherwise mostly previous .ql been suggested that ethers of the 0 gelatinization and hardening oi the mixture may o ninotrlnaine-tormaldehyde condensation prodtakeplace. i

llglts should be melted ,withr colophony lat t It ispreferahleto carry out the reaction at temneratureszot l80-220 C. Determinatidn of th peraturs between80160 C. When acid anhyuipher o1 melts thu obtained h s shown, drides or halides are used, the reaction can take however, ,withinthe innit or error these num- 15 place at lower temperatures, such as at room tembers are unwed. H'I'hereiore, it is obvious that 1 0 chemical change has been brought about, by e The reaction may be carried out in the presence process. or absence of organic solvents or diluents, such contrast to this, it has been iound Qsurpri as butanol, dipentene, benzene. when using acid that s, reaction actually tak pm 2o halides, it is preferable to work in the presence when ethersoi" the aminotrlazine-iormaldehyde 01 ac dbinding agents. such as caustic alkalis. condensation products are heated witheerbexyne p in et acids of the fatty acid series. The course or this ;I:t lsable to stop the reaction once the acid renctlon may lav-the lowerin of number ceoses to show appreciable decrease, if mas dmu htxeot newsr ader heated. at he secliq h continued be his p in the The ol carboxyiic acid react d up y reaction m ixture will flnallyselatinize and harden. the d eam the acid numb A999 Plmm n 0 the Parent materials .8 ti gos hle t .cause ircni 30.5 moi to used, the; preducts oi invention possess very o mate t lnthe edema r wrrqsemes. Oily. msmvv c u semi-sen u)v solidproducts can be s- 51 3 1 15 5 3 pmp'rfl e of jthi recurrent and or s a of E weight, products ar obtained diiy togwax-likebodies, with inclusion F 9 s ble sp'reemeeeivens vr te l al j1 1 ;he#nli lQtrifi fid fit n be read y remove by iere u' fs bf n s m r msl qh li e lmriee es ic ,d fiimqsmest a -e w e9 emcee lf-tfieseslen tnt st el -t a? nqlmibqmmgmfimQ connection, see Patents 2,193.35 u X iner a.h bufi mn ester nump rsgf n uin fl with id wm qse h m. n. an r. itcoe sm e me a d o s- .i! 9 1 ru 1i 9 u am n- 135F931. A I an quantity of .ithepr'gjhic Examples). ,Espesial emp es' 35. W mm? 1 e tolu ie; ZSPlYe-i te utane!- teesle d w c a b e Furthermore, corresponding with the aminotrianzine-formaldelrvde condensation products used as parent materials, the pure products obtained are for the most part readily hardened. By the use of heat and/or accelerators, even by allowing them to stand for an extended period, they can be converted into the insoluble state. Solutions in the lacquer solvents mentioned above are usually more resistant to self-hardening and are therefore suitable for use when applying the new substances in the lacquer industry or for other uses, etc., where the use of solutions is permissible.

By ,making use of unsaturated acids, for example, the acids of semi-drying or drying oils, products are obtained which possess air-drying properties. The speed of air-drying is greater, for example when linoleic acid is used than in the case of linseed oil itself. The drying properties may be greatly accelerated by the use of the usual dryers, an important point in the lacquer industry.

The color of the new products is very dependent on the degree of purity and the coloring power of the acids, as the aminotriazine components may generally be obtained as very pale to waterclear substances. In accordance with this, the end products usually have a brown or yellow to water-clear color.

Corresponding to the variation in properties determined by the multiplicity of patent materials, the new products can be used for the mostvaried purposes, such as crude material for burntin lacquers or air-drying lacquers, softeners and binding agents, artificial materials, surface active or water-repellent substances, etc.

In the following examples, AN stands for acid number, SN for saponification number and EN for ester number.

Example 1 270 parts of a butyl ether resin (obtained from melamine, formaldehyde and butanol according to Example 9 of Patent 2,197,357) in the form of a solution of about 83 per cent strength were first dehydrated completely, the resin being diluted with about 100 parts by volume of butanol, which was then again removed by distillation in vacuo on the oil bath. About 145 parts by volume of distillate were obtained which, in addition to the original butanol, also contained the butanol and 'water from the parent resin. The internal temperature rose to about 100? C. towards the end of the distillation.

20 parts by volume of butanol and 340 parts of stearic acid were added, and the mixture was melted whilst stirring and heating. The AN oi the mixture was 123. The reaction is continued for 2-3 hours under a good vacuum with a rising temperature of 80-130 (2., 81 parts by volume of distillate being obtained and the AN dropping to 73. The residue. amounting to about 500 parts, thus contains much stearic acid which has not yet reacted; this is removed to a large degree by repeated washing and stirring with methyl alcohol at about 40 C. After removing the methyl alcohol which remains in the washed residue by distillation, a pale-colored, balsam-like resin is obtained which is readily soluble in the usual lacquer solvents but insoluble in methyl alcohol and water. The product has the following characteristics: AN=8, SN=151, EN=143. It can be used in the artificial resin industry, especially for lacquer purposes. Evaporation of the methyl a1- cohol extracts yields 150 parts of an almost pure stearic acid, which can be used again.

Very similar products are obtained if, instead asbaseo Example 2 135 parts of a butyl ether resin of melamine (see Example 1) are dehydrated with parts by volume of butanol and are melted with an addition of 170 parts of linoleic acid. The AN drops from 132 to 95, whilst the temperature rises to 140 C. in the course of 1-2 hours. 274 parts of a viscous syrup are obtained which are worked up as described in Example 1 to remove the excess of linoleic acid. 155 parts of an end product are yielded which possesses the following characteristics: AN=10, SN=71, EN=61. The residual linoleic acid, obtained by evaporation of the methyl alcohol, is almost pure and can'be used again (131 parts).

The reaction product is a highly viscous, palecolored oil, readily soluble in lacquer solvents, insoluble in methyl alcohol and in water. Its solutions, upon evaporation, yield a coating which, even without the addition of dryers, dries more rapidly in air than linseed oil. The product can therefore be used for the manufacture of airdrying lacquers, as binding agent for burnt-in lacquers, etc.

Instead of linoleic acid, other acids of semidrying or drying oils, for example, the acids of poppy oil, cotton oil or wood oil, can be used with similar results.

Example 3 107 parts of a melamine-formaldehyde-methyl ether resin (prepared as described in Example 3 of Patent 2,202,200 and freed from mechanically mixed methyl alcohol in vacuo) are mixed with 1'10 parts of stearic acid and melted to a homogeneous mixture by heating in vacuo. The

was of this mixture is 122. The mixture is then heated for 3-4 hours, the temperature gradually rising from about C. to 135 C. and the AN dropping to about 62. The yield is 239 parts.

In order to prepare the technically pure reaction product, the fat-like, solid mass is dissolved in parts by volume of benzene, repeatedly extracted with 500 parts by volume of methyl alcohol and finally dissolved in benzene to a solution of approximately 70 per cent strength, which contains about 138 parts of the new stearic acid ester.

The product has th following propertiesr AN =5, SN=105, EN=100.

By evaporation of the methyl alcohol extracts, 103 parts of almost pure stearic acid can be reclaimed.

The butyl ether resin as used as starting material in Examples 1 and 2 may be obtained as follows:

50 parts of hexamethylolmelamine are added to 80 parts by volume of butyl-alcohol and 0.5 part by volume of concentrated hydrochloric acid and the mixture is heated toboiling for A, hour. The clear solution thus obtained is concentrated up to a dr content of 83 per cent.

asoasea The methyl ether resin as used in Example 3 may be obtained as follows:

50 parts of hexamethylolmelamine are dissolved in 150 parts by volume of methyl-alcohol in the resence of 0.2 part by volume of hydrochloric acid. As soon as solution has occurred, the same is neutralized with caustic soda solution up to the point where phenolphthalein shows a pink color. The solution is then evaporated in vacuo until it is practically tree from mechanically admixed methyl-alcohol,

Instead of the above mentioned condensation products of course also other similar condensation products mentioned in U. S. specification 2,197,357 may be used as starting materials.

What I claim is:

1. A process for the manufacture of a hardenable resinous ester, soluble in organic solvents, of an aminotrlazine-iormaldehyde condensation product, which comprises heating one molecular proportion of an ether of an aminotriazineformaldehyde condensation product with an esteriiying agent consisting oi. from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms at a temperature ranging between about 80 C. and 160 C., and terminating the reaction when the acid number ceases to show an appreciable decrease.

2. A process for the manufacture of a hardenable resinous ester, soluble in organic solvents, of a melamine-formaldehyde condensation product, which comprises heating one molecular proportion of an ether of a melamine-formaldehyde condensation product with an esterifying agent consisting of from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms at a temperature ranging between about 80 C. and 160 0., and terminating the reaction when the acid number ceases to show an appreciable decrease.

3. A hardenable resinous ester, soluble in organic solvents, of an ether of an aminotri- Mine-formaldehyde condensation product esterifled with an esterii'ying agent consisting of from about 0.5 to about 2 molecuiar proportions of a fatty acid containing at least ten carbon atoms, per molecular proportion of the ether, the esteriflcation having been terminated as soon as the acid number showed no appreciable decrease.

4. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineformaldehyde condensation product esterifled with an esteritying agent consisting of from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms. per molecular proportion of the ether, the esteriiication having been terminated as soon as the acid number showed no appreciable decrease.

5. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineiormaldehyde condensation product esterified with an esteriiying agent consisting of from about 0.5 to about 2 molecular proportions of stearic acid per molecular proportion of the ether, the esteriflcation having been terminated as soon as the acid number showed no appreciable decrease.

6. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineformaldehyde condensation product esteriiied with an esteritying agent consisting of from about 0.5 to about 2 molecular proportions of linoleic acid per molecular proportion of the ether, the esterification having been terminated as soon as the acid number showed no appreciable decrease.

GUSTAV WIDMER.

Qertificate of Correction Patent No. 2,398,569.

April 16, 1946.

GUSTAV WIDMER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, lines l-2, for ammotrianzme read ammotmazme; and line 29, for "patent read parent; and that the said Letters Patent should be read with these corrections therein th t th may conform to the record of the case in the Patent 8 0 Same Signed and sealed this 4th day of J one, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

asoasea The methyl ether resin as used in Example 3 may be obtained as follows:

50 parts of hexamethylolmelamine are dissolved in 150 parts by volume of methyl-alcohol in the resence of 0.2 part by volume of hydrochloric acid. As soon as solution has occurred, the same is neutralized with caustic soda solution up to the point where phenolphthalein shows a pink color. The solution is then evaporated in vacuo until it is practically tree from mechanically admixed methyl-alcohol,

Instead of the above mentioned condensation products of course also other similar condensation products mentioned in U. S. specification 2,197,357 may be used as starting materials.

What I claim is:

1. A process for the manufacture of a hardenable resinous ester, soluble in organic solvents, of an aminotrlazine-iormaldehyde condensation product, which comprises heating one molecular proportion of an ether of an aminotriazineformaldehyde condensation product with an esteriiying agent consisting oi. from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms at a temperature ranging between about 80 C. and 160 C., and terminating the reaction when the acid number ceases to show an appreciable decrease.

2. A process for the manufacture of a hardenable resinous ester, soluble in organic solvents, of a melamine-formaldehyde condensation product, which comprises heating one molecular proportion of an ether of a melamine-formaldehyde condensation product with an esterifying agent consisting of from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms at a temperature ranging between about 80 C. and 160 0., and terminating the reaction when the acid number ceases to show an appreciable decrease.

3. A hardenable resinous ester, soluble in organic solvents, of an ether of an aminotri- Mine-formaldehyde condensation product esterifled with an esterii'ying agent consisting of from about 0.5 to about 2 molecuiar proportions of a fatty acid containing at least ten carbon atoms, per molecular proportion of the ether, the esteriflcation having been terminated as soon as the acid number showed no appreciable decrease.

4. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineformaldehyde condensation product esterifled with an esteritying agent consisting of from about 0.5 to about 2 molecular proportions of a fatty acid containing at least ten carbon atoms. per molecular proportion of the ether, the esteriiication having been terminated as soon as the acid number showed no appreciable decrease.

5. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineiormaldehyde condensation product esterified with an esteriiying agent consisting of from about 0.5 to about 2 molecular proportions of stearic acid per molecular proportion of the ether, the esteriflcation having been terminated as soon as the acid number showed no appreciable decrease.

6. A hardenable resinous ester, soluble in organic solvents, of an ether of a melamineformaldehyde condensation product esteriiied with an esteritying agent consisting of from about 0.5 to about 2 molecular proportions of linoleic acid per molecular proportion of the ether, the esterification having been terminated as soon as the acid number showed no appreciable decrease.

GUSTAV WIDMER.

Qertificate of Correction Patent No. 2,398,569.

April 16, 1946.

GUSTAV WIDMER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, lines l-2, for ammotrianzme read ammotmazme; and line 29, for "patent read parent; and that the said Letters Patent should be read with these corrections therein th t th may conform to the record of the case in the Patent 8 0 Same Signed and sealed this 4th day of J one, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents. 

